Lene series and process of making same



named Dec. 31, 1929' UNITED ST T S PATENT "OFFICE 310mm) MICHEL, or UERDINGEN ON-THE-RHINE, GERMANY, ASSIGNOB'TO I. a. rmnnmnns'rmn AK'IIENGESELLSCHAFT, or rnaNxronr-on-rnn-Jmm, .GER-

MANY, A CORPORATION OF GERMANY CONDENSATION PROD UC'IS FBOMOLEFINES AND HYDROCABBONS OF 'THE NAPH'IHA- LENE SERIES AND PROCESS OF MAKING Ho Drawing. Original No.'1,667,214, dated April 24, 1928, Serial No. 200,500, filed June 21, 1927, and in Germany February 4, 1926. Application for reissue filed December 13, 1928. Serial'No. 825,901.

The present invention relates to the reparation of condensation products from ydrocarbons of the naphthalene series and olefines.

I have found that olefines generall will react with hydrocarbons of the napht alene series, such as, for example, naphthalene or a partially hydrogenated naphthalene compound or' other derivative thereof, at elevated temperatures, such as, for example, temperatures between about 50 C. and about 200 C. and under superatmospheric pressure, in the presence of oatalytically acting substances, whereby there are obtained homologs', or condensation products, of naphthalene. I have found, further, that,

, for effecting the aforesaid reaction, it is not necessary to use the olefines in a very concentrated state; the reaction may be effected by operating with gaseous mixtures containing olefines such as, for example, the

gaseous mixtures resulting from oil cracking operations, oilgas, and the like. Indeed, it appears that generally my new process is particularly etl'ectii e when working with gaseous mixtures containing both ethylene and the higher homologs of ethylene. While for the reaction between ethylene alone and a hydrocarbon ofthe naphthalene series it may be necessary to raise the temperature ,as high as about 200 0., I have found that in using gaseous mixturescontaining ethylene with hi her homologs, thereof the reaction can rea ily be carried out under more moderate temperature conditions, such as, for example, between about 50 C. 100 0.

Among the catalytically acting substances -tion of the olefines upon naphthalene are found to consist mainly of mono-, or poly- 'alkylated naphthalenes or higher condensaand about tion products thereof, depending largely up- 'naphthalenes proceeds, in an analogous manner. o.

The process may be illustrated by the following examples: p

Example 1 In an autoclave of 300 liters capacity 128 kg. of naphthalene and 4 kg. of aluminum chloride are stirred for some 4 hours'with ethylene under a pressure of 20 atmospheres. at from 100 to 200 C. The commencement of the reaction is advantageously promoted b passing in a little hydrogen chloride gas. The consumed ethylenei is constantly replenished from a container under pressure until a total of 38 kg. has been absorbed. After cooling the contents of the autoclave and removing the aluminum chloride, distillation is efi'ected. The first runnings contain benzine hydrocarbons, then 25 kg. of unchanged naphthalene distill over and then 110 kg. of oily product, while 25 of an undistillable residue are left behin Theoily portion boils under ordinary pressure between 250 and 400 C. consisting of a mixture of fi-mono-ethylnaphthalene, di-'* and poly-ethyl naphthalenes and binaphthyl derivatives. The quantities of these products are influenced b different variations of the above-mentione' conditions.

Example 2 'isuseda parts by weight ofmolten nap illustrated above, it has beeninbserved the hi her homologs of ethylene with the naph alene compound more readily than does ethylene alone. A furtherohservation is that the higher homologs ofethylcne exert a carrier effect in the reaction between ethylene itself and the naphthalene compound whereby, in their presence, ethylene reacts more readily and under more moderate temperature conditions.

'The reaction between naphthalene series and gaseous mixtures containing both eth lens and hi her homologs of ethylene may e illustrated b ing example.

' Ewample 3 As the mixed olefine containing gas there gas of about 30% olefine content, of which from about 20 to about 25% is eth lane and the remaining part consists of big er. homologs of ethylene. referablgbshould be free from hydrogen sulde and m water vapor; it may, however,

contain sulfur compounds other than hydrogen sulfide without particular detriment.

The gas is caused to react u ilon about 128 thalene contained 1n a pressure-tight reaction vessel in the presence of about 3.5 to 4 parts by weight 7 of aluminum chloride, ata temperature of about 80 C. and under a pressure/of from 20 to 30 atmospheres in such manner that the gas is continuously forced into the pressuretight reaction vessel while the residual gas,'-., free from or poor in, olefines,continuously is allowed to escape. After continuing this operation for a short time the reaction mixture is found to consist of about 150 parts by weight of a mixture of oils free from unnaphthalene and about 28 parts by' changed weig t of recoverable unchanged naphthalene. The mixture of oils consists almost exclusively of the homologs of naphthalene; the individual components of the oily mixtureare practically all stable and-boil without decom- 'tion. The possess great value as startng materials or the preparation of various intermediate products, and as well are foimd to be motor spiritshaving desirable properties. Y 7 V v V The process can also be carried out in such a manner that several pressure vessels charged with the naphthalene compound and catalyst are successively traversed by the crude gas containing olefines. In this manner, the process can be carried out continuousrice is intended to comprise all hydrocarbons of the y the follow The gas mixture 'ly and the olefines contained in the crude gas can thus be completely There is yet another method of working according to which the olefines mmam; r resulting from cracking processesfam a u e naphthalene in successive stages, whereby difierent products can be obtained, since the homolo of'ethylene react considerably more easily t ethylene itself.

In the following claims theterm an unsaturated hydrocarbon of the naphthalene seydrocarbons of the naphthalene series, including their homologs, with the exception of the completesly saturated hydrocarbons of the naphthalene series which correspond to the following gen- 80 eral formula: v

' x x' x x wherein X represents hydrogen or a monovalent substituent. The completely saturated hydrdtarbons of the naphthalene series have been found to beinoperative in my process.

I claim 1. Process which comprises reacting with an olefine upon an unsaturated hydrocarbon of the naphthalene series, in the presence of a catalytically] active metallic halide, under conditions of elevated temperature over 50 CI and superatmospheric pressure 2. Process which comprises reacting with an olefine upon an unsaturated hydrocarbon of the naphthalene series, in the presence of catalytically active metallic chlorides, under superatmospheric pressure and at a tempera-. tures from about 50 C. to about 200 C.

3. Process which comprises reacting with an olefinic gas containing a higher homolog of ethylene upon an unsaturated hydrocarbon of the naphthalene series, in the presence, of a catalytically acting metallic chloride, under s'uperatmospheric pressure and at a tempera: ture' of at least about 50 C. V 4. Process which comprises reacting with an olefinic gas containing ethylene and a higher homolog of ethylene, upon an unsaturated hydrocarbon of the naphthalene series, in the presence of a catalytically acting metallic chloride, under superatmospheric pressure Cand at a temperature of at least about 50 I V 53. Process which comprises reacting upon rbed bythe runs 3 to 30 atmo heres and at a temperature of about 80 6. As new products condensation products from olefines and unsaturated hydrocarbons of the naphthalene series comprising polyalkylated hydrocarbons of the naphthalene series wherein at least two of the alkyl groups of said hydrocarbons containmore than two carbon atoms. 10 7. As new products the condensation products obtainable by reacting with an olefinic gas containing a higher homolog of ethylene upon an unsaturated hydrocarbon of the na hthalene series, in the presence of a cata- 15 lytically acting metallic chloride, under superatmospheric pressure and at a temperature of at least about 50 C, the said condensa tion products comprising polyalkylated hydrocarbons of the naphthalene series, bean ing substituted by at least two ,alkyl groups containing more than two carbon atoms.

In testimony whereof, I aflix my signature. I RICHARD MICHEL. 

